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Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

Niemeyer, J., Kelly, M. J., Riddlestone, I. M., Vidovic, D. and Aldridge, S. (2015) Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides Dalton Transactions, 44 (25). pp. 11294-11305.

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Abstract

The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM[double bond, length as m-dash]B[double bond, length as m-dash]N[double bond, length as m-dash]CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines – a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)]+[BArX4]− (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; ArX = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M[double bond, length as m-dash]B metathesis reactivity with a carbodiimide, and results in Fe[double bond, length as m-dash]B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)]+[BArCl4]− (R = iPr/Cy, 16/17).

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
NameEmailORCID
Niemeyer, J.
Kelly, M. J.
Riddlestone, I. M.i.riddlestone@surrey.ac.uk
Vidovic, D.
Aldridge, S.
Date : 7 July 2015
Funders : Engineering and Physical Sciences Research Council (EPSRC)
DOI : 10.1039/c5dt00131e
Copyright Disclaimer : © The Royal Society of Chemistry 2015. Open Access Article. Published on 11 February 2015. Downloaded on 6/24/2019 11:26:46 AM. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Depositing User : Clive Harris
Date Deposited : 24 Jun 2019 10:35
Last Modified : 24 Jun 2019 10:53
URI: http://epubs.surrey.ac.uk/id/eprint/852020

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